Phenoxyethanol → Methyl 6-bromo-3-(2-phenoxyethoxy)picolinate

HRID 2178247Notes

Reaction equation

HRID 2178247 reaction equation
[Br:1][C:2]1[N:7]=[C:6]([C:8]([O:10][CH3:11])=[O:9])[C:5]([OH:12])=[CH:4][CH:3]=1.[O:13]([CH2:20][CH2:21]O)[C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1.CC(OC(/N=N/C(OC(C)C)=O)=O)C>C(Cl)Cl>[Br:1][C:2]1[N:7]=[C:6]([C:8]([O:10][CH3:11])=[O:9])[C:5]([O:12][CH2:21][CH2:20][O:13][C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)=[CH:4][CH:3]=1

Participants

5

Reactant 3

HCID 31236PhenoxyethanolHCID 5363146Diisopropyl azodicarboxylateHCID 22175135Methyl 6-bromo-3-hydroxypicolinate

Product 1

HCID 59418733Methyl 6-bromo-3-(2-phenoxyethoxy)picolinateYield 72%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

A mixture of methyl 6-bromo-3-hydroxypicolinate (26B) (308 mg, 1.33 mmol) and 2-phenoxyethanol (183 mg, 1.33 mmol) were stirred in dry DCM (10 mL). PPh3-polystyrene bound (665 mg, 2.0 mmol) was added, followed by the dropwise addition of DIAD (0.387 mL, 2.0 mmol). The mixture was stirred for 48 hours, then filtered through Celite and concentrated under reduced pressure. The crude material was purified by flash column chromatography on silica gel eluting with a gradient of PE/EtOAc 9:1-7:3 to provide 334 mg (72%) of the desired compound methyl 6-bromo-3-(2-phenoxyethoxy)picolinate (27A): 1H NMR (300 MHz, CDCl3) δ7.58-6.90 (7H, m), 4.43 (2H, m), 4.34 (2H, m), 3.91 (3H, s).

Workup

  1. additionwas added
  2. filtrationfiltered through Celite
  3. concentrationconcentrated under reduced pressure
  4. customThe crude material was purified by flash column chromatography on silica gel eluting with a gradient of PE/EtOAc 9:1-7:3

Sources & evidence

ORD record
ord-ed47b38bdc1344d4beac5208ddea2aaa
Source dataset
uspto-grants-2015_06
Patent number
US09067928B2

Reaction notes

Loading…